Substituted alpha-amino-acrylic acid nitriles



Patented Aug. I v i f Y UNITED STATES. PATENT orr csv sUBSTITUTED ALPHAAMINO-AOBYLIO ACID NITRILES Otto Nicodemus, Heinrich Lange, and HerbertKranz, Frankiort-on-the-Main, Germany, assignors, by mesne assignments.to General Aniline & Film Corporation, New York, N. Y., a corporationDelaware No Drawing. Application February 1, 1939, Se rial No. 254,006.In Germany February 3,

3.01aims. (Cl. 260293) The present invention relates to substitutedaqueous bottom layer further small quantities of a-amino-acryljc idnitrfles, nitrile may be obtained by known processes. As We have foundthat substituted c-aminoa by-product dimethylacetamide is obtained.acrylic acid nitriles may be obtained in a good The nitrile is a humidreadily mobile liquid which yield fromp-halogen-acetaldehyde-cyanhydrins on exposure to the air graduallybecomes slightly by the action of aliphatic secondary bases. Thecolored- It s a st ng od ur f b nzald hyde. course of this novelreaction is surprising. It It is readily solublein the usual organicsolvents, was expected that not only the hydroxyl group but p n ySoluble in wat r. At 22 C. its spebut also the halogen would beexchanged for an cific gravity is 0.900. The nitrile may also beamino-group. This does not 0 cur, however, but distilled at ordina y prsure W ut an essenm the amine removes hydrogen alide at the same tialloss. Boiling po under 8 r stime that it takes the place of the hydroxylsure of 759 millimeters. group. There are thus produced the hitherto un-5 0 ccof a solut on obtai ab e by sli -ins known compounds of theformula 160 cc. of anhydrous hydrocyanic acid to which CH C C=N a smallproportion of potassium" cyanide has been 15 added, together with 300grams of chloracetalde- R. hyde in 300 cc. of water at a temperature.not above +7 0., are introduced, drop by drop, into I 1210 cc. of anaqueous solution of 52 per cent v a strength of dimethylaniine. ihetemperature in 20 wherein R1 and R2 stand for alkyl groups 0 R1 theflask is kept between and by 0001- and R2 together stand for an alkylenegroup. After /2 hours the eact o 8 co p ete- The amine residue must bein tic-position be- Two layers are f r d; th t p y s s arat d. causeduring the treatment of for instance a-didried and distilled underreduced pressure. 2M3 5 methylamino-acrylic acid nitrile with water withgrams y o-ac y ac d nitrile are separation of hydrocyanic acid,dimethylacetaobtained which distils between 62 C. and 64 C. mide can beobtained in a yield of more than 50 under a pressure of 00 millimeters.The y per cent. The formation of the amide is possiamounts P centbleonly if the parent material is an; a-aminoni- 3. A solution of 420 gr ofdistilled a-hyt u droxy-p-chloropropionitrlle, obtainable as de= 30 Tha-diallgylamino-acrylic m mem a scribed in Example 1, in 34.0 cc. ofwater is added valuable intermediate products for pharmaceutidrop y p.While Stirring, tea mixture of 800 call purposes, for adjuvants in thetextile industry a s o n n r di e and 600 cc. of water. The and 12making artificial materials, temperature in the flask is kept between 25C. The following examples serve to illustrate the. d 3 C. by cooling;After 2 hours w layers 35 invention but they are not intended to limitit are The 3!. feebly y w op ayer t e t is separated, dried anddistilled under reduced 1. 270 grams of dimethylamine in an aqueous PFrom the 94111160118. (m bly turbid lut by 52 per cent t gt are dd dropbottom layer further small quantities of the reacby drop whilevigorously stirring, to 211 grams oi liiOn Product y be ta y own P essed40 4 a-hydroxy p chloropropionitrfle (obtainable by In this manner gmms0f p p y -eerylic t reaction bffl-chloracetaldehyde t anhyacid ,nitrileareobtained which distil between drous hydrocyanic acid in the presenceof a small about and about under 8 p re f proportion of potassiumcyanide and distillation 9 millimeters- Theflibld m unts to 0 Percentunder reduced pressure with neutralization of the Theu-pipelidyl-elflylic M nitrlle 1 l mpid 5 alkali), in an aqueoussolution of 90 per cent readily mobile liquid which p ly issolves instrength. By cooling, the temperature in the W ter and readily dissolvesin the usual Organic fla k is t between o C and +5. C After 2 solvents.Iinhas a characteristic odour. At 20 hours the reaction is complete. Twolayers are Chills Specific gravity 1509703- l'oomtempemiformed. The toplayer, which is of a light color, r h pr u t gradually changes colorwhereas 50 is separated, dried and distilled under redu d it remainscompletely unaltered below 0 C. like pressure. 127.5 grams ofu-dlmethylaminoe hYl 1 C 1le ci h m- Prepared acrylic acid nitrlledistilbetween 63 C. and 64 C. according to Examples 1 and 2. At ordinarytemunder a pressure of mercury oi 40 millimeters. perature it may onlybe distilled with alstron g The yield amounts to 66.5,per cent. From thedecomposition. A 35 wherein R1 and R2 stand for radicals of the gioupconsisting of alkyl radicals and alkylene radicals 10 formed by R1 andR2 togethe 2. The a-dimethylamino-acrylic acid rutrile, having a boilingpoint of about 148.5 C. under a pressure of 759 millimeters.

3. The a-piperidyl-acrylic acid nitrile, having a. boiling point betweenabout 88 C. and 89 C. under a pressure of 9 millimeters.

OTTO NICODEMUS. HEINRICH LANGE. HERBERT

